Reduced-staining colorant system

ABSTRACT

A dye composition is disclosed together with methods for its use and detergent compositions employing the combination. The dye composition is a mixture of anthraquinone dyes suitable for use with liquid laundry detergents. The composition substantially reduces the undesirable fabric staining characteristic of a detergent in which the dye is employed, while still retaining the ability to blue the fabric. Further, the color value of the detergent product is maintained at a desirable level. The composition is a combination of an oil soluble dye such as 1,4-bis(2-ethylhexylamino)-anthraquinone (C.I. Solvent Blue 58) with a water soluble dye such as 1-amino-2-sulfo, 4-(2-sulfo-para toluidino) anthraquinone sodium salt (C.I. Acid Blue 145) and/or 1,4-bis(3-sodium sulfonate mesitylidino) anthraquinone (C.I. Acid Blue 80).

This a division, of application Ser. No. 574,487, filed May 5, 1975, nowU.S. Pat. No. 3,958,928.

This invention broadly relates to a combination of selectedanthraquinone dyes for use in a liquid detergent composition. Thecombination exhibits a desirable color value coupled with reducedstaining characteristics while still retaining the ability to impart adesirable bluing effect on fabrics contacted by the detergent.

Bluing compositions such as those disclosed in U.S. Pat. No. 3,755,201are well known in the art as are liquid detergent compositions. Foresthetic reasons a blue color imparted to a liquid laundry detergent hasbeen found to be desirable and based on consumer testing, a blue producthaving a color value of a particular range is considered to be mostacceptable. When producing such products it is especially helpful if theblue colorant added to the detergent composition not only imparts adesirable blue color to the product but also assists in bluing whitefabrics which are contacted by the detergent either during washing orduring pre-wash application for specific spot or stain removal. However,in attempting to achieve a desirable product color coupled with a bluingeffect, marked undesirable staining of treated fabrics has beenobserved. The amount of staining has been found to correlate with thetype of dye used, the fabric treated, specific adjuvants utilized withthe detergent product and various substances that have come into contactwith the fabric during its normal use.

Anionic dyes, for example, are found to be particularly susceptible tomany common detergent additives. If the dye is changed to an oil solubletype and used in sufficient concentration to retain the desirable colorvalue, the above problem can be eliminated for certain fabrics, forexample, cotton. However, with synthetic fabrics, for example urethanebased fabrics, the staining problem with the increased amount of oilsoluble dye becomes considerable. Thus, the difficulty of producing anacceptably colored liquid detergent which retains a bluing capabilityand has reduced staining characteristics is apparent.

Since a large variety of synthetic fabrics including urethane basedfabrics as well as many common additives to which anionic dyes aresusceptible are currently employed in the consumer market, it is thusseen to be extremely desirable to produce a colored, estheticallypleasing liquid detergent product, which is usable in consumer orientedsituations on common synthetic and natural fabrics.

Accordingly, it is an object of this invention to provide a combinationof dyes for use with a liquid detergent composition which provides anesthetically pleasing product of a desirable color value; has thecapacity to blue fabrics and has substantially reduced stainingcharacteristics.

Another object is to overcome or substantially reduce the problems ofthe prior art heretofore described.

Other objects and advantages will appear as the description proceeds.

The attainment of the above objects is made possible by the utilizationof a combination of selected anthraquinone dyes in a liquid detergentcomposition comprising about 0.006 to about 0.025% by weight of a dyemixture consisting essentially of about 0.0005% to about 0.0025% of1,4-bis(2-ethylhexylamino)-anthraquinone and a water solubleanthraquinone dye selected from the group consisting of 1-amino-2-sulfo,4-(2-sulfo-para toluidino) anthraquinone sodium salt; 1,4-bis (3-sodiumsulfonate-mesitylidino) anthraquinone and mixtures thereof; about 5 toabout 85% by weight of a synethic organic detergent and about 15 toabout 95% by weight of compounds selected from the group consisting ofbuilders, fillers, solvents and adjuvants.

By employment of the present invention, the above objects are achieved,together with the advantage that a pleasantly colored consumeracceptable liquid detergent composition can be utilized withoutsubstantial staining, in conjunction with common fabrics and commondetergent additives.

Generally, the type of dyes used are a combination of two or morecolorants with different staining characteristics each at a sufficientlyreduced concentration to achieve some bluing while keeping staining atan acceptable level. A suitable combination is an anionic water solubledye with an oil soluble dye. More specifically, a combination of##STR1## with either or both of ##STR2## and ##STR3## is used.

The total concentration of the dye combination utilized is generallygoverned by production of the required color value, together with thedesirable bluing effect which effect is in turn produced by the oilsoluble component (Formula I). The color value and bluing effects mustbe achieved without substantial staining of synthetic fabrics. Otherconsiderations are stability, solubility, economics and compatabilitywith detergent compositions.

Thus, the total amount of the combination of the dye of Formula I witheither or both of the dyes of Formulae II and III is about 0.006% toabout 0.025% by weight, preferably about 0.008% to about 0.012% byweight. The specific amounts of each which may be employed areconsidered hereinafter.

An additional factor to be considered in determining the proper totalamount to produce a desired color value is whether the detergent is inthe form of an emulsion or a solution. Emulsions, having a relativelyopaque milky appearance, generally require more dye to produce a givencolor value than do solutions.

Broadly, the amounts of each of the individual components used aresufficient enough to provide a medium blue color value to a liquiddetergent composition, to contribute some bluing effect to fabrics andnot to visibly stain fabrics.

The preferred color value is initially determined by consumer preferencetests. Based on data gathered from these tests, it is determined that aGardner Reflectometer "b" reading of -5.0 to -15.0 is acceptable while a"b" reading of -7.0 to -10.0 is preferred. The range of color values aredetermined on a Gardner XL-10 CDM Reflectometer using a 2.0 "b" (i.e.yellow and blue range) standard plate.

The individual components of the combination are generally used in thefollowing amounts:

Formula I from about 0.0005% to about 0.0030% by weight, preferably0.0015% to 0.0025% by weight.

Formula II from about 0.005% to about 0.025% by weight, preferably about0.006% to about 0.012% by weight.

Formula III from about 0.005% to about 0.025% by weight, preferablyabout 0.006% to about 0.012% by weight.

If the amounts of each employed is too low, then the color value of theproducts will be too low and if excess amounts are used, staining willresult.

The weight ratio of Formula I to either or both of Formulae II and III,which is employed, is thus about 1 part by weight of Formula I to about10 parts by weight of either or both of Formulae II and III to about 1part by weight of Formula I to about 50 parts by weight of either orboth of Formulae II and III.

The fabrics that may be treated with the compositions of this inventioninclude those formed from all of the commonly used natural and syntheticfibers such as, for example, cottons, wools, silk, polyesters, linen,acetates, nylons, rayons, synthetic blends, and polyurethanes, such asspandex, as well as blends of natural and synthetic fibers such ascotton-polyester blends.

The detergent compositions which are used with the instant invention areliquid compositions either in emulsion or solution form, but can beextended to be included in formulations that take other forms as well,such as powders, bars, sticks, tablets, flakes, beads or other formsthat are generally known in the detergent art. These detergents commonlycontain at least one detergent active compound; a builder such as, forexample, tetrasodium pyrophosphate, opacifiers, thickening agents andthe like, various adjuvants, solvating agents and in the case ofemulsified detergents, emulsifiers.

Particularly preferred compositions utilizing the dye combination ofthis invention are as follows:

    ______________________________________                                        Nonionic detergent preferably an                                                                   0 to about 40% by wt.                                    alcohol, ethylene oxide adduct                                                having 8 to 15 carbon atoms                                                   and 7-12 E.O. groups                                                          Alkali metal or organic amine                                                                      about 5 to about 20%                                     salts of alkyl aryl sulfonates                                                                     by wt.                                                   Builders             0 to about 30% by wt.                                    Hydrotropes          about 3 to about 10%                                                          by wt.                                                   Stabilizers          0 to about 10% by wt.                                    Adjuvants            0 to about 5% by wt.                                     Water                balance to 100%                                          ______________________________________                                    

In detergent compositions, in which the mentioned dye mixtures arepreferably employed, the active detersive ingredient is preferably anonionic detergent. Preferred compositions of this type are also anionicdetergents. Mixtures of such materials and amphoterics may also be used.

the nonionic synthetic organic detergents are usually condensationproducts of organic aliphatic or alkyl aromatic hydrophobic compoundsand hydrophilic lower alkylene oxide groups. A wide variety ofhydrophobic compounds which include carboxy, hydroxy, amido or aminogroups having a free hydrogen on the nitrogen can be condensed, with alower alkylene oxide or equivalent, such as ethylene oxide, polyethyleneoxide, or polyethylene glycol to form the nonionic detergents. Usefulhydrophobes are higher aliphatic alcohols, middle alkyl phenols, higherfatty acids, carboxamides, mercaptans and sulfonamides. The ethyleneoxide condensates of such materials usually include from 5 to 50 molesof ethylene oxide but as many as 200 moles may often be present. Thehydrophobic groups will generally contain at least about 6 carbon atomsbut may contain as many 50. A preferred range is from about 8 to 30carbon atoms in the hydrophobe. The ethylene oxide or the correspondingglycols or poly- derivatives thereof are preferred but other loweralkylene oxides, such as propylene oxide, may also be of use and in somecases butylene oxide can be employed, generally in minor proportions.Other nonionic compounds include as active detersive ingredients are thepolyoxyalkylene esters of higher fatty acids which will generallycontain from 12 to 30 moles of ethylene oxide per mole of fatty acid of10 to 22 carbon atoms. The alkylene oxide condensates of higher fattyacid amides are useful and these will usually have present from 10 to 50moles of ethylene oxide per mole of 8 to 22 carbon atom fatty acidgroup. Corresponding carboxamides and sulfonamides are ulso useful.Oxyalkylated higher aliphatic alcohols are especially preferred nonioniccompounds, utilizable in conjunction with the linear higher alkylbenzene sulfonate anionic detergents. The fatty alcohols will usuallyhave from 10 to 18 carbon atoms and the polyxoyethylene group willcontain from 6 to 30 moles of ethylene oxide, preferably from about 6 to12 moles thereof when the alcohol is of 12 to 16 carbon atoms. Suchnonionics are sold as Neodols by Shell Chemical Co.

Hydrophobic groups of the nonionics can be made by condensingpolyoxypropylene or polyoxybutylene radicals, in which case thesubsequent condensation with ethylene oxide or polyoxyethylene groupsresults in the production of a nonionic detergent such as those soldunder the names Ucon and Pluronic. In the Pluronics the block copolymersmade are of ethylene oxide, propylene oxide and some propylene glycoland have a molecular weight in the range of about 1,000 to 15,000. Thepolyethylene oxide content thereof will usually be from 20 to 80 percentby weight and the preferred hydrophobic moiety weight is from about1,0000 to 4,000. Nonionics may be derived by the condensation ofethylene oxides with the reaction product of propylene oxide andethylene diamine, in a manner similar to that employed for thepreparation of the Pluronics. Various other nonionic detergents whichmay be used include the ethylene oxide adducts of monoesters ofhexahydric alcohols and inner ethers thereof, with the higher fattyacids being of about 10 to 20 carbon atoms, e.g., sodium monolaurate,mannitan monopalmitate. Additional nonionic detergents that have beenfound to be very useful are the amine oxide of the general formula R¹ R²R³ N O, wherein R¹ is a higher alkyl of 10 to 20 carbon atoms and R² andR³ are lower alkyls. Similar compounds wherein the nitrogen is replacedby phosphorus are also useable.

Although usually not employed in detergent compositions, amphotericdetergents are useful. These are generally water soluble salts ofderivatives of aliphatic amines which contain at least one cationicgroup, e.g., quaternary ammonium, non-quaternary nitrogen or quaternaryphosphonium, one or two alkyl groups of about 8 to 18 carbon atoms andan anionic water solubilizing carboxyl sulfo, sulfato, phosphato orphosphono group. The groups may be straight chained or branched and thecationic nitrogen or phosphorus may be in a heterocyclic ring. Examplesof such amphoteric detergents include the alkyl beta-aminopropionates,the alkyl betaiminodipropionates, the alkyl and hydroxyalkyl taurinatesand the long chain imidazole derivatives, such as those described inBritish Pat. No. 1,412,921 and U.S. Pat. Nos. 2,773,068, 2,781,354 and2,781,357. Preferred detergents of this type are sodium N-laurylbeta-aminopropionate and disodium N-lauryl iminodipropionate.

The anionic detergents will normally contain from 8 to 26, preferably 10to 20 carbon atoms in a higher organic organic hydrophobic group, andwill have present at least one water-solubilizing radical selected fromthe group consisting of sulfonates, sulfates, carboxylates, phosphatesand phosphonates, to produce a water soluble detergent. Examples ofsuitable anionic detergents are water soluble sulfated and sulfonatedsynthetic detergents containing an alkyl radical of 8 to 20, preferably12 to 18 carbon atoms. Such radical may be a portion of a higher acylgroup. Preferred examples of sulfonated anionic detergents are thehigher alkyl aromatic sulfonates, such as the linear higher alkylbenzene sulfonates containing from 10 to 18 atoms in the higher alkylgroup. Branched chain materials may also be used, but are not preferred.The sodium, potassium, ammonium and lower alkanolamine salts of suchsulfonic acids are preferred. In some cases, higher alkyl toluenesulfonates and higher alkyl naphthalene sulfonates may be beneficiallyemployed. Of the linear alkyl benzene sulfonates, those of 12 to 15carbon atoms in the chain and wherein the salt forming cation is sodiumare much preferred. These usually will be terminally or 2-substituted onthe benzene ring. However, other points of joinder to the benzene may beemployed and the main factor in producing a successful detergent of thistype is to have the chain linear so as to promote biodegradability ofthe product.

Included among other anionic detergents which may be employed are theolefin sulfonates, e.g., long chain alkene sulfonates, long chainhydroxyalkane sulfonates and mixtures thereof. These are usually of 8 to25 carbon atoms, preferably of 12 to 20 carbon atoms. Also useful arethe paraffin-derived sulfonates containing about 10 to 20, preferably 15to 20 carbon atoms. Examples of the primary paraffin sulfonates made byreaction of long chain alpha olefins with bisulfites and those compoundshaving the sulfonate group distributed along the paraffin chain. Sodiumand potassium sulfates of higher alcohols containing 8 to 18 carbonatoms, such as sodium lauryl sulfate and sodium tallow alcohol sulfatemay be employed, as may be the sodium and potassium salts ofalpha-sulfofatty acid esters of 10 to 20 carbon atoms in the acyl group,e.g., methyl alpha-sulfomyristate and methyl alphasulfotallowate. Thesodium and ammonium sulfates of mono- and diglycerides of higher fattyacids, e.g., coconut oil fatty acids monoglyceride monosulfate, stearicdiglyceride monosulfate, are also useful, as are the sulfatedcondensation products of polyethyoxyethanols with fatty alcohols and thesulfonates of higher alkyl glycerol ethers. The alkyl phenyl polyethoxyether sulfates having about 1 to 6 oxyethylene groups per molecule areuseful anionic detergents when the alkyls are of about 7 to 9 carbonatoms. Such a range of carbon atoms is considered as "middle" alkyl.Other useful anionic detergents include the higher acyl sarcosides,isethionates and N-methyl taurides. These detergents, while normallyused as their ammonium, alkanolamine, or alkali metal salts, may oftenbe employed as soluble alkaline earth metal salts. The water solublesalts, e.g., the sodium, ammonium and alkanolamine salts, of higherfatty acids containing about 8 to 20 carbon atoms, preferably 10 to 18carbon atoms, are good anionic detergents, too. The suitable fatty acidsfor making such soaps can be obtained from animal and vegetable oils,fats and waxes, e.g., tallow, grease, coconut oil, tall oil and variousmixtures thereof. Preferred are the sodium soaps of the fatty acidsderived from the mixture of coconut oil and tallow.

Cationic surface active agents are usually avoided in the presentdetergent compositions but may be employed when there are no anionicspresent or when a laundry treating composition is used primarily for itsantibacterial activity. Examples of the cationic detergents are thenormal primary amines wherein the alkyl group is of 12 to 15 carbonatoms, and the corresponding diamines. Quaternary ammonium compounds ofthe known type, preferably those having one or two higher alkyl groupsand two or three lower alkyl groups attached to the nitrogen and whereinthe solubilizing anion is a halogen are also useful, as are equivalentquaternaries of high anti-bacterial activity, which are well known inthe art.

Detergent compositions in which the present dyes are incorporated mayalso have present builder salts, fillers, solvents and adjuvants.Typical of the builders that may be employed are the organic buildersalts, such as carboxymethyloxysuccinic acid and other buildersdisclosed in U.S. Pat. No. 3,692,685; the inorganic builders such as thealkali metal polyphosphate salts, e.g., pentasodium tripolyphosphate,tetrasodium pyrophosphate and the corresponding potassium compounds.Other builders, especially popular in formulations low in phosphatecontent, are alkali metal silicates and carbonates, as well as thecorresponding borates and bicarbonates. Preferably, the silicates willhave an Na₂ O:SiO₂ ratio of about 1:2.35, although the range of 1:2 to1:3 is normally useful and often ratios as low as 1:3.2 are acceptable.Other organic builders that are employed are the citrates, diglycolates,gluconates, ethylene diamine tetraacetic acid, sodium salt and trisodiumnitrilotriacetate. Of course, mixtures of builders may be used and theymay be supplemented with fillers, which generally do not perform anysignificantly useful function with respect to increasing the detergencyof the product. Among the fillers that are useful are the sulfates,chlorides, nitrates, and acetates, usually as their alkali metal salts,e.g., sodium sulfate. Solvents that may be employed will usually beprimarily aqueous and any supplementing solvent material will generallybe a lower alcohol, e.g., ethanol, isopropanol, or a polyol, e.g.,polyethylene glycol, glycerol, if present at all. Of course, otherorganic solvent may be present, as in emulsions.

The various adjuvants that are used, in addition to the dye combinationinclude germicides, fungicides, perborate bleaches, enzymes, soilsuspending agents, fabric softeners, thickeners, corrosion inhibitors,sequestrants, tarnish inhibitors, perfumes and various other materialintended to improve the functional and aesthetic properties of thedetergents. Such materials are well known in the art and need not bedescribed at length here. Perborate bleaches and enzymes, while notcurrently compatible with most aqueous system due to hydrolysis, may beapplicable should problems in this area be resolved.

Among the additives for detergent compositions are materials which maybe employed alone in other laundry preparations with the present dyemixtures. Soil suspending materials, e.g., sodium carboxymethylcellulose, methyl cellulose and hydroxypropyl methyl cellulose may be indetergent or presoak compositions. Useful bactericidal effects may beobtained by adding germicides to the detergent or by utilizing these inseparate treatments after washing has been completed. Fabric softeningcompositions may be employed in a similar manner.

Lengthy descriptions of additional softeners are not given hereinbecause all such compounds may be colored with the present mixed dyesand descriptions thereof may be found in the reference, "Detergents andEmulsifiers" 1974 Annual, by J. W. McCutcheon. Of course, the fabricsofteners and bactericides may also contain various adjuvants, such asthose previously described.

In addition, if a detergent in the form of an emulsion is desired, thiscan be accomplished by incorporation of a stabilizer, as disclosed inU.S. Pat. Nos. 3,629,125 and 3,544,122, to maintain the active andbuilder components in the aqueous medium without allowing substantialphase separation.

The stabilizer preferred comprises a combination of a linear and across-linked copolymer of ethylene and maleic anhydride and is employedin the liquid detergent in an amount sufficient to provide both thedesired stability and viscosity of the product. A suitable level of thiscombination of copolymers ranges from about 0.60% to about 0.9% byweight of the total composition.

Suitable linear copolymers of ethylene and maleic anhydride areavailable from the Monsanto Chemical Co. under the designations"EMA-21," "EMA-31," "EMA-4118", etc. Cross-linked copolymers areavailable under the designations "EMA-61," "EMA-71", "EMA-81," "EMA-91,"and similar materials in this series. In general, the monomers arepolymerized in a 1:1 ratio, the resins having molecular weights rangingfrom about 1500 and upwards. The cross-linked copolymers are generallycross-linked with a diamine, and alkylene polyamine, or a diolefinicmaterial such as an ether, ester or a hydrocarbon, etc. Examples ofpolyamine cross-linking agents include diethylene triamine, triethylenetetramine, tetraethylene pentamine, and higher molecular weightpolyethylene polyamines. Exemplary diolefinic cross-linking agentsinclude divinyl benzene, diallyl ether, diallyl esters and the like.Other suitable cross-linking agents are set forth in U.S. Pat. Nos.3,165,486 and 3,235,505 of Monsanto Company and include the preferredvinyl esters of olefinically unsaturated aliphatic carboxylic acidshaving from 3 to 24 carbon atoms, e.g., vinyl crotonate, vinyllinoleate, divinyl itaconate, vinyl acrylate and the like. The linearand cross-linked copolymers which have been successfully utilized inpreparing formulations of this invention include the following:

    ______________________________________                                                      specific                                                                      Viscosity*                                                                             Molecular weight                                       ______________________________________                                        Linear resin:                                                                 EMA-21          0.6        Intermediate.                                      EMA-31          1.0        High.                                              EMA-4118        1.8        Very high.                                                         Viscosity                                                                     in cps.**                                                     Cross-linked resin:                                                           EMA-61          12,000                                                        EMA-71          40,000                                                        EMA-81          80,000                                                        EMA-91          160,000                                                       ______________________________________                                         *Determined on a 1% solution of the resin in dimethyl formamide at            25° C.                                                                 **Measurements made at 25° C on a 1% aqueous solution, adjusted to     pH 9 with ammonium hydroxide, using a Brookfield viscometer, No. 6 spindl     at 5 r.p.m.                                                              

The following Examples will more fully illustrate the embodiments ofthis invention. All parts, percentages and proportions referred toherein and in the appended claims are by weight unless otherwiseindicated.

EXAMPLE 1

A liquid detergent is prepared having the following composition:

    ______________________________________                                        Anionic Active                                                                              NaLAS 17% by weight                                             Nonionic Active                                                                             Neodol 25-9 7% by weight                                        Builder       Sodium Citrate Dihydrate, 10% by wt.                            Hydrotrope    Sodium xylene sulfonate6% by wt.                                              sodium toluene sulfonate  ≈4:1                          Buffer        Monoethanolamine, 2% by wt.                                     Adjuvants     Cross-linked polystyrene copolymer                                            Latex opacifier, 0.05% by wt.                                                 Anti-redeposition agent, methyl                                               cellulose, 0.5% by wt.                                                        Perfume, .15% by wt.                                                          Fluorescent Dyes, .085% by wt.                                  Colorant      Formula I - 0.002% by wt.                                                     Formula III - 0.0051% by wt.                                    Water         Balance to 100%                                                 ______________________________________                                    

1000 grams of the liquid detergent of the above formula is prepared inthe following manner.

100 ml of demineralized water is introduced into a vessel. 0.051 gramsof the dyestuff of Formula III and 5 grams of Methocel A-100 are addedto the water with moderate stirring. The temperature is adjusted to110°-120° F and this mixture is allowed to stir for approximately 1hour. At the end of this time, the temperature is reduced to 65°-75° F.141 grams of a 41.55% aqueous solution of sodium xylene sulfonate andsodium toluene sulfonate in a ratio of 4 parts xylene sulfonate to onepart toluene sulfonate are added. 54 grams of a 50% aqueous solution ofsodium hydroxide and 179.9 grams of 89% active linear dodecylbenzenesulfonic acid are then added to the solution vessel. A premixcomposition is prepared consisting of 70 grams of Neodol 25-9, 0.02grams of the dyestuff of Formula I, 1.03 grams of fluorescent dyes, and0.75 grams of stearic acid. The premix is then added to the solution inthe vessel. 250 grams of a 40% aqueous solution of sodium citrate,dihydrate is added slowly, followed by 20 grams of monoethanolamine,1.25 grams of a 40% solids content opacifying agent, and 1.5 grams ofperfume. Demineralized water is added to 1000 grams ond the pH of thesolution is adjusted with sodium hydroxide to 11.2.sup.± 0.2. Moderatemixing is maintained throughout all additions.

EXAMPLE II

An emulsified liquid detergent is prepared with the followingcomposition:

    ______________________________________                                        Nonionic Active                                                                             Neodol 25-9 8% by weight                                        Builder       Tetrapotassium/tetrasodium                                                    pyrophosphate 8.05/1 25%                                        Hydrotrope    Sodium xylene sulfonate2% by wt.                                              Sodium toluene sulfonate  ≈4:1                          Buffer        NaSilicate 2.4 ratio 3% by wt.                                  Adjuvants     Stabilizing resin ethylene                                                    maleic anhydride copolymer .8%                                                Perfume, 0.1%                                                                 Fluorescent Dyes, 0.1%                                          Colorant      Formula I - 0.002                                                             Formula II - 0.005                                                            Formula III - 0.006                                             Water         Balance to 100%                                                 ______________________________________                                    

1000 grams of the above formulation is prepared in the following manner.

200 ml of water and 48 grams of a 41.55% aqueous solution of sodiumxylene sulfonate and sodium toluene sulfonate in a ratio of 4 partsxylene sulfonate to 1 part toluene sulfonate are introduced into avessel and maintained with vigorous high shear mixing. A first premix isprepared containing 80 grams of Neodol 25-9, 0.02 grams of the dyestuffof Formula I and 0.5 grams of a fluorescent dye. This premix is added tothe mixing solution in the vessel. The pH of this mixture is maintainedat less than 3 and the temperature is adjusted to 170° F.

2.0 grams of EMA-21 and 6.0 grams of EMA-61, both of which aretrademarks for ethylene maleic anhydride copolymers marked by MonsantoChemical Company, are added and the mixture is then allowed to hydratefor one hour at 170° F under vigorous mixing. 18 grams of a 45.5%aqueous solution of potassium hydroxide and 441.8 grams of a 56.6%aqueous solution of an 8.05 to 1 mixture of tetrapotassium pyrophosphateand tetrasodium pyrophosphate is added.

64 grams of 48% aqueous solution of 2.4 to 1 ratio Na₂ 0 to SiO₂ sodiumsilicate and 5 grams of sodium carboxymethylcellulose thickening agentis then added. A second premix is prepared containing 0.76 grams of afluorescent dye, 0.5 grams of potassium hydroxide and 10 ml of water.This second premix is added together with 0.05 grams of the dyestuff ofFormula II and 0.06 grams of the dyestuff of Formula III. 1.0 grams ofperfume and a sufficient amount of water to make 1000 grams are thenadded and the pH is adjusted as necessary with potassium hydroxide to11.9.sup.± 0.2. Vigorous high shear mixing and a temperature of 170° Fis maintained.

Throughout the preparation and when the preparation is complete, themixture is passed through a homogenizer as 1700 to 2000 P.S.I. toprepare the final emulsion.

EXAMPLE III

A liquid detergent is prepared having the following composition:

    ______________________________________                                        Nonionic Active                                                                             Neodol 25-9 8% by weight                                        Builder       Sodium citrate dihydrate, 20%                                   Hydrotrope    Sodium xylene sulfonate2% by wt.                                              Sodium toluene sulfonate  ≈4:1                          Buffer        NaSilicate 2.4 ratio, 10% by wt.                                Adjuvants     Stabilizing resin ethylene                                                    maleic anhydride copolymer, 85%                                               Perfume, 0.1%                                                                 Fluorescent Dyes, 0.1%                                          Colorant      Formula I - 0.003                                                             Formula II - 0.008                                              Water         Balance to 100%                                                 ______________________________________                                    

The composition of Example III is prepared in exactly the same manner asthat of Example II, except that the phosphate builder is replaced by acitrate builder, the silicate level is increased and varying amounts ofthe other components are employed.

EXAMPLE IV

A series of products were prepared as in Example II utilizing variouscombinations of the dyes of this invention as well as control products.The products are subjected to two tests, an overnight soak test and asandwich staining test which are described as follows.

OVERNIGHT SOAK TEST

The overnight soak test is run by taking 4 liquid ounces of the product,dissolving it in one gallon of demineralized water and allowing swatchesof various fabrics to soak overnight at room temperature in thesolution. The following day the switches are rinsed in a washing machineon a rinse cycle for roughly 15 minutes, dried for about 2 hours andsubsequently evaluated. The temperature used for washing is 120° F.

SANDWICH STAINING TEST

The sandwich staining test is utilized to determine whether intimatecontact of a detergent with a fabric will cause staining. This isespecially significant if the detergent is utilized for pre-treatment ofspots or stains. The liquid detergent is placed dropwise onto a dryswatch of fabric, the product is allowed to penetrate the swatch forabout 5 minutes and then folded and allowed to stand overnight. Theswatch is unfolded, the excess product removed by blotting and theswatch is washed in tap water with the product at the recommended uselevel. The temperature used is 120° F.

A series of fabrics are utilized for this test ranging from cotton clothto synthetics and synthetic blends.

The specific dye combinations utilized are presented in Table I and theresults of the tests performed are presented in Table II. The evaluationis done visually using numerical values of 0, 2, 4, 6 and 8. O isrepresentative of no staining and 8 is representative of considerablestaining.

                  TABLE I                                                         ______________________________________                                        DYE COMBINATIONS USED FOR TESTING                                             AS REPORTED IN TABLE II                                                       Colorant                                                                      System                                                                        ______________________________________                                        1      Formula I  0.007%   (Control)                                          2      Formula II 0.0165%  (Control)                                          3      Formula III                                                                              0.02%    (Control)                                          4      Formula I  0.003%   Formula III                                                                             0.01%                                    5      Formula I  0.003%   Formula II                                                                              0.008%                                   6      Formula II 0.008%   Formula III                                                                             0.01%                                                                         (Control)                                7      Formula I  0.002%   Formula II                                                                              0.005%                                          Formula III                                                                              0.006%                                                      8      Formula I  0.002%   Formula III                                                                             0.012%                                   9      Formula I  0.002%   Formula III                                                                             0.008%                                   10     Formula I  0.002%   Formula III                                                                             0.016%                                   11     Formula I  0.002%   Formula III                                                                             0.02%                                    ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        SANDWICH AND OVERNIGHT SOAK TESTS                                             Colorant System                                                               Sandwich Staining Test                                                        Material  1     2     3   4   5   6   7   8   9   10  11                      ______________________________________                                        Terry     0     0     0   0   0   0   0   0   0   4   0                       Spandex   2     0     0   0   0   0   0   2   0   0   0                       Wool      0     0     0   0   0   0   0   0   0   0   0                       Spun Nylon                                                                              2     0     0   0   0   0   0   0   0   0   0                       Banlon    2     0     0   0   0   0   0   0   0   0   0                       Wool Flannel                                                                            0     0     0   0   0   0   0   0   0   0   0                       Colorant System                                                               Overnight Soak Tests                                                          Material  1     2     3   4   5   6   7   8   9   10  11                      ______________________________________                                        Terry     0     0     0   0   0   0   0   0   0   4   0                       Spandex   6     0     0   2   2   0   0   2   0   0   0                       Wool      0     4     0   0   2   0   0   0   0   0   0                       Spun Nylon                                                                              4     0     0   0   0   2   0   0   0   0   0                       Banlon    2     0     0   0   2   0   0   0   0   0   0                       Wool Flannel                                                                            0     4     0   0   2   0   0   0   0   0   0                       ______________________________________                                    

As a result of the tests reported in Table II, it can be seen that thecombination of dyes of this invention, i.e. the dye of Formula Itogether with either or both of the dyes of Formulae II and III providesignificantly less staining on fabric.

EXAMPLE V

The preferred color value of the products of this invention isdetermined by consumer preference testing of color values and thencorrelation of these preference tests with a numerical scale on aReflectometer.

A Gardner XL-10 CDM Reflectometer is used and "b" (i.e. yellow and blue)readings are taken. A 250 ml beaker is placed over the light source anda 2.0 "b" standard plate is placed over the mouth of the beaker. Thereading of the Reflectometer is then set at 0.0 corresponding to thestandard, for convenience. A sufficient amount of product, 100 drops, tocover the bottom of the beaker is then added. The standard plate isagain placed over the mouth of the beaker and the "b" reading is taken.Results of these tests are reported in Table III. The more negativevalues represent a deeper blue.

                  TABLE III                                                       ______________________________________                                        REFLECTOMETER COLOR VALUE READINGS                                            Colorant System                                                                             Test 1   Test 2   Test 3 Mean                                   ______________________________________                                        No colorant (Control)                                                                       8.8      9.9      9.2    9.3                                    .0035% Formula I                                                                            -2.7     -1.6     -2.7   -2.3                                   .007% Formula I                                                                             -8.5     -8.7     -9.2   -8.8                                   .002/.02% Formula I/                                                                        -11.8    -12.8    -11.6  -12.1                                  Formula III                                                                   ______________________________________                                    

These values are taken from an emulsified detergent and thereforerequired relatively greater amounts of dye to achieve an acceptablecolor value. A detergent which is a solution requires correspondinglyless dye.

EXAMPLE VI

The bluing effect of the dye combination of this invention is determinedin comparison with an uncolored product and with each of the dyes of thecombination used separately. This comparison is accomplished bypreparing a composition as in Example II and incorporating varyingamounts of the dyestuff combinations of this invention therein and bypreparing control formulations as in Example II which contain nocolorant and each of the dyes of Formulae I, II and III, respectively.

The liquid detergent compositions are prepared as in Example II andvarying amounts of colorants are incorporated therein as specified inTables IV and V.

26.25 grams of the formulation is added to three gallons of deionizedwater at 120° F in a stainless steel tub containing a mechanicalagitator, similar to that in a commercial washing machine. The water andformulation are agitated for one minute to achieve complete dispersionof the composition.

A series of 12 inch × 12 inch swatches of different fabric are added asfollows:

a) Cotton Shirting TF 429*

b) Cotton Toweling (Startex)

c) Nylon Taffeta TF 302A*

d) Spun Dacron TF 754 AW*

e) Polyester Double Knit TF 720*

f) 65/35 Dacron/Cotton blend with a Permanent Press Finish TF 7406 WRL*.

The load is then made up to 16 ounces with cotton sheeting TF 400*.

The load of swatches in the tub is agitated for 15 minutes. The rub isthen drained and the load is rinsed with agitation for 3 minutes. Thewashing rinsing cycle is carried out 5 times and the swatches are handsqueezed between each wash and rinse and at the end of each rinse. Thefabric swatches are then ironed and their blue-yellow reflectancemeasured on a Gardner XL-10 CDM Reflectrometer using a "b" reading. TheReflectometer is standardized by using a Gardner standard plate with a"b" value of +0.2.

The results of the tests are reported in Tables IV and V where the morenegative values indicate greater bluing effect.

                                      TABLE IV                                    __________________________________________________________________________    BLUING TESTS                                                                                      "b" Values - 5 Washes                                                         Cotton                                                                             TF302A TF754AW                                       Product             Startex                                                                            Nylon  Spun Dacron                                   __________________________________________________________________________    1. 0.002%/0.008% Formula I/Formula III                                                            +3.1 +2.3   +3.1                                          2. 0.002%/0.02% Formula I/Formula III                                                             +3.2 +3.1   +3.2                                          3. 0.007% - Formula I (Control)                                                                   +3.0 +1.2   +1.5                                          4. No Colorant      +3.7 +4.2   +3.9                                                                   TF7406WRL                                                                TF429                                                                              Dacron/                                                                              TF720                                                             Cotton                                                                             Cotton Polyester                                     Product             Shirting                                                                           Blend  Double Knit                                   __________________________________________________________________________    1. 0.002%/0.008% Formula I/Formula III                                                            +2.2 +3.1   +3.3                                          2. 0.002%/0.02% Formula I/Formula III                                                             +2.6 +3.1   +3.4                                          3. 0.007% Formula I (Control)                                                                     +2.6 +0.6   +2.3                                          4. No Colorant      +2.9 +3.6   +3.9                                          __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________    BLUING TEST                                                                                      "b" Values - 5 Washes                                                                              TF7406WRL                                                                TF429                                                                              Dacron/                                                                              TF720                                             Cotton                                                                            TF302A                                                                             TF754AW                                                                              Cotton                                                                             Cotton Polyester                      Product            Startex                                                                           Nylon                                                                              Spun Dacron                                                                          Shirting                                                                           Blend  Double Knit                    __________________________________________________________________________    Formula II - 0.165% (Control)                                                                    +3.1                                                                              +3.8 +2.7   +2.6 +3.9   +3.7                           Formula III - 0.02% (Control)                                                                    +2.8                                                                              +4.7 +2.7   +3.2 +3.7   +3.8                           Formula I - 0.002%/Formula II - 0.005%                                                           +3.0                                                                              +3.8 +2.1   +2.8 +2.9   +3.5                           Formula III - 0.006                                                           Formula I - 0.003%/Formula II - 0.008%                                                           +3.1                                                                              +3.1 +1.9   +2.4 +2.4   +3.3                           No Colorant (Control)                                                                            +3.2                                                                              +4.4 +2.6   +2.5 +3.7   +3.7                           Formula I - 0.007% (Control)                                                                     +2.9                                                                              +2.7 +1.1   +2.6 +1.7   +3.0                           __________________________________________________________________________

The results of the tests performed in Example VI and reported in TablesIV and V clearly show that the dye combination of this invention retainsa bluing effect in comparison to an uncolored product or a productincorporating only the dye of Formula I. A comparison of the colorvalue, staining, and bluing characteristics of the dye mixture of thisinvention with the color value, staining and bluing characteristics ofthe dye of Formula I alone shows that the dye mixture of the inventionhas a desirable color value, retains a bluing capacity but hassubstantially reduced staining characteristics.

In view of the preceeding description and examples, variousmodifications thereof will be suggested to those skilled in the art andare to be included within the spirit and purview of this application andthe scope of the appended claims.

What is claimed is:
 1. A method for producing a synthetic liquiddetergent having a Gardner Reflectometer "b" color value of about -5 to-15 whereby said liquid detergent exhibits reduced stainingcharacteristics while still retaining the ability to impart bluing tofabrics comprising admixing with said detergent a sufficient amount toproduce said color value of a dye mixture consisting essentially ofabout 0.0005% to about 0.0030% by weight of 1,4-bis (2ethylhexylamino)anthraquinone and at least one water solubleanthraquinone dye selected from the group consisting of 1-amino-2-sulfo,4-(2-sulfo-para toluidino) anthraquinone sodium salt, 1,4-bis(3-sodiumsulfonate-mesitylidino)anthraquinone and mixtures thereof.
 2. A methodas defined in claim 1 wherein said dye mixture is present in an amountof about 0.008% to about 0.012% by weight, said dye mixture consistingessentially of about 0.0015% to about 0.0025% by weight of1,4-bis(2-ethyl-hexylamino) anthraquinone and at least one water solubleanthraquinone dye selected from the group consisting of about 0.005% toabout 0.025% by weight of 1-amino-2-sulfo, 4-(2-sulfopara toluidino)anthraquinone sodium salt, about 0.005% to about 0.025% by weight of1,4-bis(3-sodium sulfonate-mesitylidino) anthraquinone and mixturesthereof.
 3. A method as defined in claim 1 wherein said dye mixture is0.002% by weight of 1,4-bis(2-ethylhexylamino) anthraquinone and 0.005%by weight of 1,4-bis(3-sodium sulfonate-mesitylidino) anthraquinone.